EP0871552A1 - Procede d'obtention de revetements multicouches - Google Patents

Procede d'obtention de revetements multicouches

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Publication number
EP0871552A1
EP0871552A1 EP96944002A EP96944002A EP0871552A1 EP 0871552 A1 EP0871552 A1 EP 0871552A1 EP 96944002 A EP96944002 A EP 96944002A EP 96944002 A EP96944002 A EP 96944002A EP 0871552 A1 EP0871552 A1 EP 0871552A1
Authority
EP
European Patent Office
Prior art keywords
weight
meth
acrylate
coating composition
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96944002A
Other languages
German (de)
English (en)
Other versions
EP0871552B1 (fr
Inventor
Gudrun Wiemann
Lutz Gross
Götz-Ekkehard SAPPER
Joachim Woltering
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP0871552A1 publication Critical patent/EP0871552A1/fr
Application granted granted Critical
Publication of EP0871552B1 publication Critical patent/EP0871552B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to a method for producing multilayer coatings on a substrate surface in which
  • the substrate is generally first coated with an electrophoretic paint and / or intermediate stone chip primer, a fuller coat or a first base coat layer, which may be pigmented and then using a lacquer containing at least one pigment, a base lacquer layer is applied and this base lacquer layer is optionally overcoated with a transparent lacquer.
  • the single-layer or multi-layer lacquer obtained in this way is then baked about 20 to 30 ⁇ m well covering
  • the object of the present invention is to provide a method for producing multilayer coatings and a method for repairing multilayer coatings on a substrate surface, in which well-covering coatings are obtained by using a special aqueous base coating composition with small layer thicknesses, it is desirable that this is suitable for both plain and metal or mica effect lacquers.
  • the base coating composition used should continue to be compatible with conventional clear lacquers, such as, for example, aqueous or solvent-containing clear lacquers or powder clear lacquers, and these clear lacquers should be applied to the basecoat can be made without it being compared to conventional tional paint systems comes to a deterioration in the appearance of the paint system.
  • the present invention accordingly relates to a method for producing a multilayer coating on a substrate surface in which
  • an aqueous base coating composition (ii) which contains an aqueous polymer dispersion as film-forming agent is applied to a substrate surface coated with an aqueous base coating composition (i),
  • the base coating compositions (i) and (ii) are baked together with the top coating composition, characterized in that the base coating composition (ii) is an aqueous
  • Polymer dispersion contains (x) an acrylate polymer based on 30 to 60% by weight of -C 8 alkyl (meth) acrylate monomers, 30 to 60% by weight of vinyl aromatic monomers and 0.5 to 10 % By weight (meth) acrylic acid and
  • Y a non-associative thickener which contains an acrylate copolymer based on (-C-C 6 ) alkyl (meth) acrylate and (meth) acrylic acid.
  • Another object of the present invention is a method for repairing multi-layer coatings, wherein
  • a basecoat film (II) is repaired with an aqueous coating composition (ii) which contains an aqueous polymer dispersion as film-forming agent,
  • step (E) the coating obtained in step (D) is coated with a suitable transparent top coating composition
  • the coating composition (ii) is cured together with the top layer, characterized in that the base coating composition (ii) contains an aqueous polymer dispersion containing
  • Polymer dispersion contains (x) an acrylate polymer and (y) a thickener that contains an acrylate copolymer.
  • the acrylate polymer of component (x) used according to the invention can contain the linear and branched chain derivatives as CrC 8 -alkyl (meth) acrylate monomer units, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl and Isopropyl (meth) acrylate, n-butyl and isobutyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferred.
  • (Meth) acrylamide monomers and their derivatives can also be present as further monomers.
  • vinyl aromatic monomers e.g. Styrene, ⁇ -alkyl styrene and vinyl toluene can be used.
  • the acrylate polymer can be prepared by processes known from the prior art, for example emulsion polymerization.
  • the acrylate polymer is preferably used in the form of a dispersion. During the manufacturing process, this will be
  • the quantitative ratio between the monomers and the water is preferably set so that the resulting dispersion has a solids content of 30 to 60% by weight, preferably 35 to 60% by weight, and can be used directly for the preparation of the base coating composition.
  • a particularly suitable acrylate polymer is commercially available as an aqueous dispersion under the name Acronal 290 D (BASF AG; Ludwigshafen).
  • an anionic emulsifier is preferably used alone or as a mixture with others as the emulsifier.
  • anionic emulsifiers are the alkali metal salts of sulfuric acid half-esters of alkylphenols or alcohols, furthermore the alkali metal salts of sulfuric acid half-esters of oxyethylated alkylphenols or oxyethylated alcohols, preferably the alkali metal salts of sulfuric acid half-ester of a nonylphenol or 4-mole ethylene oxide or non-reacted Aryl sulfonate, sodium lauryl sulfate, sodium lauryl ethoxylate sulfate and secondary sodium alkane sulfonates, the carbon chain of which contains 8-20 carbon atoms.
  • the amount of the anionic emulsifier is 0.1 to 5.0% by weight, based on the monomers, preferably 0.5 to 3.0% by weight.
  • a nonionic emulsifier of the ethoxylated alkylphenol or fatty alcohol type for example an addition product of 1 mol of nonylphenol and 4 to 30 mol
  • Ethylene oxide can be used in a mixture with the anionic emulsifier.
  • the glass transition temperature of the acrylate polymer is preferably between 15 ° C and 35 ° C, particularly preferably between 20 ° C and 25 ° C.
  • the acrylate polymer used according to the invention preferably has a number-average molar mass (determination: gel permeation chromatography using polystyrene as the standard) from 200,000 to 2,000,000, preferably from 300,000 to 1,500,000.
  • acrylate copolymers with non-associative groups are used as the thickener component (rheological aid) (y) in the base coating composition, the groups being (C 1 -C 6 ) -alkyl (meth) acrylate and (meth) acrylic acid as monomer units contain.
  • a preferred copolymer contains (meth) acrylic acid and at least two different (-CC 6 ) -alkyl (meth) acrylate monomers as monomer units.
  • the (meth) acrylic acid is present in the copolymer preferably in amounts from 40% by weight to 60% by weight, particularly preferably from 46% by weight to 55% by weight, based on the amount of the entire copolymer .
  • the (-C 6 ) alkyl (meth) acrylate monomer I is preferably in amounts of 30% by weight to 50% by weight, in particular 36% by weight to 46% by weight, and the (meth) acrylate polymer II preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, in each case based on the amount of the entire copolymer.
  • Rheological aids should give the base coating composition the desired viscosity, in particular at the pH, which is generally alkaline.
  • a particularly preferred thickener when present as a dispersion, is thin and thickens at a neutral or basic pH.
  • the acrylate copolyer is suitably used as a finished dispersion. Dispersions of this type preferably contain fatty alcohol alkoxylates, in particular C 8 -C 2 2 fatty alcohol ethoxylates.
  • a be- particularly suitable acrylate copolymer dispersion is commercially available under the name Viscalex HV 30 (Allied Corporation, Great Britain).
  • the thickener in the base coating composition used according to the invention is preferably in an amount of 0.5 to 5.0% by weight, in particular approximately 0.3 to 1.5
  • the thickener is usually used as a dispersion with a concentration of 15 to 45% by weight, preferably 20 to 35% by weight.
  • the coating agent according to the invention can also contain epoxy-functional and / or carboxyl-functional constituents, such as conventional glycidyl compounds, e.g. Glycidyl acrylate or glycidyl methacrylate polymers.
  • Suitable carboxyl-functional crosslinkers are, for example, carboxylic acids, in particular saturated, straight-chain, aliphatic dicarboxylic acids having 3 to 20 carbon atoms in the molecule, dodecane-1, 12-diacid being used with preference.
  • the crosslinkers can also be used to modify the properties
  • Polyvinyl alcohol can also be used as a further auxiliary binder. It has been found that the addition of polyvinyl alcohol in an amount of up to 10% by weight, preferably from 1 to 5% by weight, can improve the compatibility with the top coating compositions applied to the base coating composition. Polyvinyl alcohol has a solvent-repellent effect, so that any solvent or other components which may be present in the top coating composition cannot penetrate into the base coating composition and change color due to the repellent effect of the polyvinyl alcohol.
  • crosslinkers known in the paint field such as melamine resins, which can react with free OH groups, can be used as further crosslinkers.
  • the base coating compositions can also contain other compatible water-thinnable resins, such as, for example, aminoplast resins, polyesters, polyurethanes and also acrylated polyurethanes and urethanized acrylates, which are used to achieve certain coating properties, such as adhesion and generally as grind resins for pigments.
  • the auxiliary binder and / or the crosslinking agent can be used in an amount of up to 10% by weight, in particular from 0.5 to 10% by weight.
  • the base coating compositions (ii) used according to the invention generally have a solids content of about 15 to 60% by weight.
  • the solids content varies with the intended use of the coating compositions.
  • metallic paints for example, it is preferably 17 to 25% by weight.
  • plain-colored paints it is higher, for example 30 to 45% by weight.
  • Ammonia and / or amines can be used to neutralize components (x) and (y)
  • aqueous coating agent is usually adjusted to a pH between 6 and 9, preferably 7 to 8.5.
  • the base coating composition (ii) may contain organic solvents in an amount up to 15% by weight.
  • suitable organic solvents are naphthalenes, gasolines and alcohols.
  • the base lacquers according to the invention can contain alkylene glycols, such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,4-hexanediol, 6, neopentyl glycol and other diols, such as dimethylolcyclohexane, as further liquid components.
  • the base coating composition (ii) can contain as pigments customary pigments used for painting automobile bodies, such as e.g. Effect pigments as well as organic and inorganic coloring pigments.
  • suitable effect pigments are commercially available aluminum bronzes, the aluminum bronzes chromated according to DE-OS 36 36 183, commercially available stainless steel bronzes as well as other conventional metal flakes and metal flake pigments and non-metallic effect pigments, such as e.g. Pearlescent or interference pigments.
  • coloring pigments on an inorganic basis examples include titanium dioxide, iron oxides and carbon black.
  • coloring pigments on an organic basis examples include indanthrene blue, cromophthal red, irgazin orange, sicotrans yellow, heliogen green and others
  • Corrosion protection pigments, such as zinc phosphate may also be present.
  • the base coating composition (ii) can also contain fillers customary in the field of paint chemistry. These include silica, magnesium silicate, talc, titanium dioxide and barium sulfate.
  • the proportion of pigments and fillers in the coating composition according to the invention can total 5 to 25% by weight, based on the solids content.
  • the pigment can be added in any manner, e.g. as an aqueous slurry or as a paste.
  • the pigments can, for example, with a grinding resin (auxiliary binder, dispersing agent and
  • pigments In the case of plain-colored lacquers, it is preferred to suspend the pigments in dispersing agents and water. If aluminum or flakes are used, these are optionally slurried in a mixture of water and surfactant and possibly solvent or rubbed in the main binder or in another auxiliary binder.
  • the pigment pastes should preferably be made without solvents.
  • component (x) can vary depending on the pigment used. If the pigments are organic and / or inorganic color pigments, component A is preferably present in an amount of 25 to 50% by weight, based on the solids content. If the pigments are effect pigments, component A is preferably present in an amount of 15 to 30% by weight, based on the solids content.
  • the base coating composition may contain film-forming aids as a further component.
  • film-forming aids are dicarboxylic acid dialkyl esters, 1,2-propylene glycol, high-boiling gasolines and naphthalenes, which have a boiling point above 100 ° C., preferably above 140 ° C.
  • the base coating composition can optionally contain further auxiliaries and additives.
  • auxiliaries are catalysts, auxiliaries, defoamers, dispersion auxiliaries, wetting agents, preferably carboxy-functional dispersants, anti-oxidants, UV absorbers, radical scavengers, leveling agents, biocides and / or water retention agents.
  • the base coating composition (ii) is applied to a substrate surface coated with an aqueous base coating composition (i).
  • aqueous base coating composition (i) As watery
  • Base coating composition (i) is preferably a lacquer layer formulation which a) contains a water-thinnable polyurethane resin as binder which comprises a Acid number from 10 to 60 and a number average molecular weight from 4000 to 25000 and can be produced by aa) a polyester and / or polyether polyol with a number average molecular weight from 400 to 5000 or a mixture of such polyester and / or Polyether polyols, bb) a polyisocyanate or a mixture of polyisocyanates, cc) a compound which has at least one group which is reactive towards isocyanate groups and at least one group capable of forming anions in the molecule, or a mixture of such compounds and, if appropriate, dd) one Organic compound containing hydroxyl and / or amino groups with a molecular weight of 40 to 400 or a mixture of such compounds are reacted with one another and the reaction product formed is at least partially neutralized, and b) contains pigments and / or
  • a lacquer layer formulation is produced on the basis of a physically drying polyurethane dispersion without polyester and aminoplast resins. It was found that the use of a lacquer consisting only of polyurethane resins and pigments leads to a material which can be used particularly well as a filler and intermediate layer of stone chipping, since it is unexpectedly stable against mechanical loads, in particular stone chipping and impact.
  • Component (a) can be prepared from aa), bb), cc) and optionally dd) by the methods of polyurethane chemistry which are well known to the person skilled in the art (cf. for example US Pat. No. 4,719,132, DE-OS 3628124, EP-A) -89497, EP-A-256540 and WO 87/03829).
  • Saturated and unsaturated polyester and / or polyether polyols in particular polyester and / or polyether diols with a number average molecular weight of 400 to 5000, can be used as component (aa).
  • Linear or branched polyether diols such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols, are mentioned as examples.
  • the selected polyether diols should not introduce excessive amounts of ether groups, otherwise the polymers formed will swell in water.
  • the preferred polyether diols are poly (oxypropylene) glycols in the molar mass range M n from 400 to 3000.
  • Polyester diols are produced by esterification of organic dicarboxylic acids or their anhydrides with organic diols or are derived from a hydroxy carboxylic acid or a lactone.
  • polyols can be used in small amounts Scope polyols or polycarboxylic acids with a higher valency are used.
  • the dicarboxylic acids and diols can be linear or branched aliphatic, cycloaliphatic or aromatic dicarboxylic acids or diols.
  • the diols used to prepare the polyesters consist, for example, of alkylene glycols, such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, 6, neopentyl glycol and other diols, such as dimethylolcyclohexane.
  • alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, 6, neopentyl glycol and other diols, such as dimethylolcyclohexane.
  • polyols such as trimethylolpropane, glycerol, pentaerythritol
  • the acid component of the polyester consists primarily of low molecular weight dicarboxylic acids or their anhydrides with 2 to 30, preferably 4 to 18, carbon atoms in the molecule.
  • Suitable acids are, for example, o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaric acid, hexachloroheptane dicarboxylic acid, and tetrachlorophthalic acid or fatty acid / tetrachlorophthalic acid.
  • their anhydrides if they exist, can also be used.
  • Smaller amounts of carboxylic acids with 3 or more carboxyl groups for example trimellitic anhydride or the adduct of maleic anhydride with unsaturated fatty acids, can also be present in the formation of polyester polyols.
  • Polyester diols obtained by reacting a lactone with a diol can also be used. These are characterized by the presence of terminal hydroxyl groups and recurring polyester fractions of the formula (-CO- (CHR 2 ) n -CH 2 -O).
  • n is preferably 4 to 6 and the substituent R 2 is hydrogen, an alkyl, cycloalkyl or alkoxy radical.
  • the substituents can have up to 18 carbon atoms. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.
  • Has value 4 and all R substituents are hydrogen, preferred.
  • the reaction with lactone is started by low molecular weight polyols, such as ethyl glycol, 1,3-propanediol, 1,4-butanediol, dimethylcyclohexane.
  • polyols such as ethyl glycol, 1,3-propanediol, 1,4-butanediol, dimethylcyclohexane.
  • other reaction components such as ethylenediamine, alkyldialkanolamines or even urea
  • polylactam diols are also suitable as higher molecular weight diols, which are produced by reacting, for example, ⁇ -caprolactam with low molecular weight diols.
  • Aliphatic and / or cycloaliphatic and / or aromatic polyisocyanates can be used as component bb).
  • aromatic polyisocyanates can be used as component bb).
  • Phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, biphenylene diisocyanate, naphthylene diisocyanate and diphenylmethane diisocyanate isocyanate.
  • (cyclo) aliphatic polyisocyanates Due to their good resistance to ultraviolet light, (cyclo) aliphatic polyisocyanates produce products with a low tendency to yellowing. Examples include isophorone diisocyanate, cyclopentylene diisocyanate, and hydrogenation products of aromatic diisocyanates such as cyclohexylene diisocyanate, methylcyclohexylene diisocyanate and dicyclohexylmethane diisocyanate.
  • Aliphatic diisocyanates are compounds of the formula OCN- (CR 3 2 ) r -NCO, in which r is an integer from 2 to 20, in particular 6 to 8, and R 3 , which may be the same or different, is hydrogen or a lower alkyl radical with 1 represents up to 8 carbon atoms, preferably 1 to 2 carbon atoms.
  • examples of these are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, dimethylethylene diisocyanate, methyl trimethylene diisocyanate and trimethylhexane diisocyanate.
  • Isophorone diisocyanate and dicyclohexylmethane diisocyanate are particularly preferred as diisocyanates.
  • Component bb) must be composed in terms of the functionality of the polyisocyanates in such a way that no crosslinked polyurethane resin is obtained.
  • component bb) can also contain a proportion of polyisocyanates with functionalities over two - such as Triisocyanants - included. Products which have been found to be suitable as triisocyanates are those obtained by trimerization or oligomerization of diisocyanates or by reaction of diisocyanates with compounds containing polyfunctional OH or NH groups.
  • These include, for example, the biuret of hexamethylene diisocyanate and water, the isocyanurate of hexamethylene diisocyanate or the adduct of isophorone diisocyanate with trimethylolpropane.
  • the average functionality can be reduced if necessary by adding monoisocyanates. Examples of such chain terminating monoisocyanates are phenyl isocyanate, cyclohexyl isocyanate and stearyl isocyanate.
  • the polyurethane resin a) should have an acid number of 10 to 60, preferably 20 to 35.
  • the amount of groups capable of forming anions to be introduced into the polyurethane molecules can be calculated from the acid number.
  • Groups capable of forming anions are introduced into the polyurethane molecules by incorporating compounds cc) into the polyurethane molecules which contain at least one group which is reactive toward isocyanate groups and one which is capable of forming anions in the molecule.
  • Suitable groups reactive toward isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups.
  • Suitable groups capable of forming anions are carboxyl, sulfonic acid and / or phosphonic acid groups, carboxyl groups being preferred.
  • Component cc) can be used, for example, alkanoic acids with two substituents on ⁇ -carbon atoms.
  • the substituent can be a hydroxyl group, an alkyl group or preferably an alkylol group.
  • These alkanoic acids have at least one, generally 1 to 3 carboxyl groups in the molecule. They have two to about 25, preferably 3 to 10, carbon atoms.
  • Examples of component cc) are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid.
  • alkanoic acids are the ⁇ , ⁇ -dimethylolalkanoic acids of the general formula R 4 - C (CH 2 OH) 2 COOH, where R 4 represents a hydrogen atom or an alkyl group with up to about 20 carbon atoms.
  • Examples of such compounds are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolpentanoic acid.
  • the preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid.
  • Compounds containing amino groups are, for example, ⁇ , ⁇ -diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluene sulfonic acid and 2,4-diamino-diphenyl ether sulfonic acid.
  • the preferably used polyurethane resins a) can optionally be prepared using organic compounds containing hydroxyl and / or amino groups and having a molecular weight of 40 to 400, or a mixture of such compounds (component dd)).
  • component dd leads to an increase in the molecular weight of the polyurethane resins.
  • polyols with up to 20 carbon atoms per molecule such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butylene glycol, 1,6-hexanediol, trimethylolpropane, castor oil or hydrogenated castor oil , Di-trimethylolpropane ether, pentaerythritol, 1, 2-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol A, bisphenol F, neopentylglycol, hydroxypivalic acid neopentylglycol ester, hydroxyethylated or hydroxypropylated
  • Bisphenol A hydrogenated bisphenol A and mixtures thereof are used.
  • the polyols are generally used in amounts of up to 30% by weight, preferably 2 to 20% by weight, based on the amount of components aa) and dd) used.
  • Di- and / or polyamines with primary and / or secondary can also be used as component dd)
  • Polyamines are essentially alkylene polyamines having 1 to 40 carbon atoms, preferably about 2 to 15 carbon atoms. They can carry substituents that have no hydrogen atoms that are reactive with isocyanate groups. Examples are polyamines with a linear or branched aliphatic, cycloaliphatic or aromatic structure and at least two primary amino groups.
  • the diamines are hydrazine, ethylenediamine, propylenediamine, 1,4-butylenediamine, piperazine, 1,4-cyclohexyldimethylamine, hexamethylenediamine-1,6, trimethylhexamethylenediamine,
  • Preferred diamines are hydrazine, alkyl- or cycloalkyldiamines, such as propylenediamine and 1-amino-3-aminomethyl-2,5,5-trimethylcyclohexane. It can also be used as a polyamine
  • Component dd are used which contain more than two amino groups in the molecule. In these cases, however, e.g. by using monoamines to ensure that no crosslinked polyurethane resins are obtained.
  • Such useful polyamines are diethylenetriamine, triethylenetetramine, dipropylenetriamine and dibutylenetriamine.
  • An example of a monoamine is ethylhexylamine.
  • component a) is part of the prior art and is e.g. in US-PS 4719132, DE-OS 3628124, EP-A-89497, EP-A-256540 and WO 87/03829 described in detail.
  • Ammonia and / or amines (in particular alkylamines), amino alcohols and cyclic amines, such as di- and triethylamine, dimethylaminoethanolamine, diisopropanolamine, morpholine, N-alkylmorpholine, can be used to neutralize component a). Volatile amines are preferred for neutralization. It is particularly important to observe the weight ratio of binder to pigment or filler. This is preferably between 0.5: 1 and 1.5: 1. The range between 0.6: 1 and 1.2: 1 is preferred.
  • Talc has proven itself as a pigment or filler. Its share in the total amount
  • Pigments and fillers are 20 to 80% by weight. The range from 30 to 70% by weight is preferred.
  • aminoplasts in small quantities. These should not be more than 10% by weight based on the total amount of the base coating composition (i). It is better to stay below 5% by weight.
  • Resins of this type are well known to the person skilled in the art and are offered by many companies as sales products.
  • Amino plastic resins are condensation products made from aldehydes, in particular formaldehyde and, for example, urea, melamine, guanamine and benzoguanamine.
  • the aminoplast resins contain alcohol, preferably methylol groups, which are generally partially or preferably completely etherified with alcohols.
  • Water-thinnable amino resins, in particular water-thinnable melamine-formaldehyde resins, are preferably used.
  • Polyisocyanate crosslinking agents can also be contained in the coating layer formulation. Their proportions are usually below 30% by weight, preferably below 10% by weight. The crosslinking reactivity is generally lower than 130 degrees Celsius.
  • the use of the preferably applicable coating composition (i) described above permits considerably lower layer thicknesses than comparable materials according to the prior art. These are far below 35 ⁇ m, i.e. regularly below 15 ⁇ m. Despite this small layer thickness, resistance to stone chipping is achieved, which corresponds to layer thicknesses of 35 ⁇ m and more.
  • the base coating composition (i), optionally after predrying at about 70 ° C., can be applied to the base coating composition (ii) and then a transparent one
  • Top coating can be applied.
  • the coating thus obtained is then baked in a manner known per se, preferably at a temperature between 130 and 160 ° C. If the color of the base coating composition (i) is matched to the color of the base coating composition (ii), it is even possible to reduce the layer thicknesses even further without any loss of quality.
  • the described basecoat composition (i) can contain all auxiliaries and additives known per se in paint technology, as were mentioned for the basecoat composition (ii).
  • the base coating composition (ii) is applied to the substrate in a manner known per se, for example by spraying, brushing, dipping, flooding, knife coating or rolling, e.g. Metal, plastic, wood or glass applied.
  • the base coating composition (ii) may optionally be applied to the
  • Coating (i) with water to adjust the solids content solvents or rheology aids to adjust the application properties and, if appropriate, a base to regulate the pH. If the viscosity is not yet in the desired range, rheology aids (y) or further thickeners, if appropriate in an amount of 0.01 to 0.06% by weight, based on the solids content, can be added.
  • the base coating compositions applied to the substrate in stage (A) are overcoated with a suitable transparent top coating composition in stage (B) of the process according to the invention.
  • the top coating is advantageously allowed to evaporate briefly, preferably 1 to 15 minutes, in particular 4 to 8 minutes, at a temperature of 60 to 100 ° C., preferably 70 to 85 ° C.
  • the period of evaporation depends on the temperature and can be set over a wide range.
  • Particularly stable multilayer coatings can be obtained if the substrate obtained in step (A) is dried.
  • the drying is preferably carried out to the extent that there is sufficient filming or crosslinking of the base layer (ii) so that water and / or solvents which may be present in the top coating composition applied in step (B) are not incorporated into the Base layer (ii) can diffuse.
  • top coats can be applied as a transparent top coating composition.
  • the clear lacquers used in the field of lacquer chemistry are preferred, such as clear lacquers based on water or solvents, powder clear lacquers, powder coatings.
  • slurry clearcoats, solvent-borne and aqueous two-component clearcoats, etc. are used, powder slurry clearcoats being particularly preferred.
  • the transparent top coating composition can be applied by conventional methods known in the art.
  • Another object of the present invention is accordingly a multi-layer coated substrate, the coating being applied to the substrate surface by
  • the coating compositions (i) and (ii) are stoved together with the top coating composition, characterized in that the base coating composition (ii) is an aqueous
  • the coating composition can be cured at ambient temperature. When cured at ambient temperature, the above-mentioned baking time is extended accordingly, including the two-component clearcoat used, between about 15 and 24 hours. A special aid or a specific device for curing this coating composition is therefore not necessary. Examples
  • one of the above-described aqueous polyurethane dispersions is dissolved in with deionized water, a commercially available leveling agent based on a water-dilutable acrylate resin, with a solution of a commercially available antifoam based on an unsaturated branched diol Butyl diglycol and N, N-dimethylethanolamine were added and pasted with post-treated titanium dioxide of the rutile type and surface-treated talc and a standard lampblack.
  • This mixture is divided into a discontinuous Laboratory sand grinder filled and dispersed until a fineness of max. 10 ⁇ m in the Hegmann grindometer is reached.
  • Aqueous lacquers are then produced from the dispersing mixtures with the addition of further polyurethane resin dispersion and butyl diglycol. These with N, N-dimethylethanolamine to a pH of 7.2 to 7.5 and with deionized water to a spray viscosity of 33 see (DIN 4) can be set.
  • Aerosil R972 (Degussa) 0.20 0.20 0.20
  • the pH of the mixture obtained was adjusted to 8.0 with dimethylethanolamine (DMEA).
  • the viscosity of the paint obtained was adjusted to 110 mPas using 25 parts by weight of water.
  • the solids content was 18.85%.
  • Example 2.2 A. In a reaction vessel 22 parts by weight water, 2 parts by weight of sol were submitted Vesso ® 200 (C ⁇ o-C 3 -Aromatengemisch) and 1 part by weight of butyl glycol. 25 parts by weight of Acronal 290 D (aqueous dispersion, solids content 50.0%) were added with stirring.
  • Vesso ® 200 C ⁇ o-C 3 -Aromatengemisch
  • butyl glycol 25 parts by weight of Acronal 290 D (aqueous dispersion, solids content 50.0%) were added with stirring.
  • Viscalex HV 30 (solids content 30.6%).
  • the pH of the mixture obtained was adjusted to 8.0 with 0.4 part by weight of dimethylethanolamine (DMEA).
  • DMEA dimethylethanolamine
  • a clear powder coating material based on a glycidyl methacrylate-containing binder and dodecanedioic acid were dispersed in 25 parts by weight of water and ground to a particle size of less than 5 ⁇ m.
  • the mixture obtained in B was stirred into the dispersion obtained in D with vigorous stirring.
  • the aluminum slurry obtained in C was then added portionwise to the resulting mixture.
  • the viscosity of the paint obtained was adjusted to 110 mPas using 25 parts by weight of water.
  • the solids content was 18.35%.
  • a paint preparation was prepared according to the procedure described in Example 2, with the exception that in step D 10 parts by weight of a powder clear coat based on a binder containing glycidyl methacrylate and dodecanedioic acid in 20 parts by weight
  • the solids content was 20.35%.
  • the pH of the mixture obtained was adjusted to 8.0 with 0.4 part by weight of dimethylethanolamine (DMEA).
  • DMEA dimethylethanolamine
  • the mixture obtained in B was stirred into the dispersion obtained in D with vigorous stirring.
  • the aluminum slurry obtained in C was then added portionwise to the mixture obtained.
  • the solids content of the paint was 26.83%.
  • Lusolvan FBH * commercial product from BASF AG, Ludwigshafen
  • the pH of the mixture obtained was adjusted to 8.0 with dimethylethanolamine (DMEA).
  • the pH of the mixture obtained was adjusted to 8.0 with dimethylethanolamine (DMEA).
  • Paste (pigment content 43.2% by weight), 1.17 parts by weight of Disperbyk * 190 (dispersing agent) and 0.03 part by weight of Viscalex HV 30 (solids content 30.6%) were dispersed and ground to a particle size below 5 ⁇ m.
  • the mixture obtained in B was stirred into the dispersion obtained in D with vigorous stirring.
  • the pigment paste obtained in C was then added in portions to the mixture obtained.
  • the solids content was 28.06%.
  • Example 2.8 The procedure described in Example 6 was repeated, except that 20 parts by weight of Acronal 290 D (aqueous dispersion, solids content 50.0%) in step A and 10 parts by weight of a clear powder coating material based on a binder containing glycidyl methacrylate and dodecanedioic acid in step D were used.
  • Acronal 290 D aqueous dispersion, solids content 50.0%
  • the pH of the mixture obtained was adjusted to 8.0 with dimethylethanolamine (DMEA).
  • Paste (pigment content 43.2% by weight), 1.17 parts by weight of Disperbyk * 190 (dispersing agent) and 0.03 part by weight of Viscalex HV 30 (solids content 30.6%) were dispersed and ground to a particle size below 5 ⁇ m.
  • the mixture obtained in B was stirred into the dispersion obtained in D with vigorous stirring.
  • the pigment preparation prepared in step B was then stirred in.
  • the solids content was 29.04%.
  • the coating compositions listed in Table I were applied in an order with a dry film thickness of 15 ⁇ m to phosphated steel sheet coated with a commercially available electrocoat using an electrostatic high-speed rotation system (Behr Ecobell, 45000 rpm, outflow rate: 120 ml / min, voltage: 60 kV) che injected.
  • the application was carried out at an air temperature of 23 degrees Celsius and a relative air humidity of 60%.
  • the sprayed panels were 10 min. at 23
  • the basecoat layer obtained in this way was overcoated electrostatically with an aqueous powder clearcoat dispersion.
  • the entire paint was then baked for 2 minutes at 23 ° C., 5 minutes at 50 ° C. and at 140 ° C. for 30 minutes.
  • the coatings obtained showed a very good flow, covered the structure of the electrocoating very well and showed good intermediate adhesion to the electrocoating primer.
  • the stone chip resistance of the coatings produced according to the invention is at least as high as the stone chip resistance of coatings which have been produced in accordance with DE-A-4005961.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention a pour objet un procédé d'obtention d'un revêtement multicouche sur la surface d'un substrat, selon lequel (A) on applique comme couche de base (II), sur une surface du substrat enduite d'un revêtement de base aqueux (i), une composition de revêtement aqueuse (ii) renfermant, comme agent filmogène, une dispersion polymère aqueuse, (B) on sèche la composition appliquée à l'étape (A), (C) on applique sur la couche de base (II) ainsi obtenue une composition formant une couche de recouvrement transparente appropriée, et (D) on effectue la cuisson des couches de base (I) et (II) conjointement avec la couche de recouvrement. Ce procédé est caractérisé en ce que la composition de revêtement de base (ii) renferme une dispersion polymère aqueuse contenant (x) un polymère acrylate à base de 30 à 60 % en poids de monomères d'alkyl (C1-C8)(méth)acrylate, 30 à 60 % en poids de monomères vinylaromatiques et 0,5 à 10 % en poids d'acide (méth)acrylique, et (y) un épaississant à effet non associatif, renfermant un copolymère acrylate à base d'alkyl (C1-C6)(méth)acrylate et d'acide (méth)acrylique.
EP96944002A 1995-12-21 1996-12-18 Procede d'obtention de revetements multicouches Expired - Lifetime EP0871552B1 (fr)

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DE19547943 1995-12-21
DE19547943 1995-12-21
PCT/EP1996/005693 WO1997023307A1 (fr) 1995-12-21 1996-12-18 Procede d'obtention de revetements multicouches

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EP0871552A1 true EP0871552A1 (fr) 1998-10-21
EP0871552B1 EP0871552B1 (fr) 2000-07-12

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JP (1) JP4141498B2 (fr)
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AT (1) ATE194513T1 (fr)
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DE10009913B4 (de) * 2000-03-01 2004-12-23 Basf Coatings Ag Verfahren zur Herstellung von Mehrschichtlackierungen auf elektrisch leitfähigen Substraten und deren Verwendung
DE10040223C2 (de) * 2000-08-17 2002-12-05 Basf Coatings Ag Strukturviskose, von organischen Lösemitteln und externen Emulgatoren freie Pulverklarlack-Slurry, Verfahren zu ihrer Herstellung und ihre Verwendung
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US6511740B2 (en) * 2000-12-06 2003-01-28 Toray Plastics (America), Inc. Inline coated polyester film with thermally stable and releasable coating
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JP3904463B2 (ja) 2002-02-12 2007-04-11 日本ペイント株式会社 自動車用水性ベース塗料組成物
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ES2912030T3 (es) * 2012-08-28 2022-05-24 Basf Coatings Gmbh Polímero en barnizados de varias capas que dan color y/o que dan efecto
JP6689749B2 (ja) * 2013-12-18 2020-04-28 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 多層塗装系を製造する方法
CA2930882C (fr) * 2013-12-18 2022-05-31 Basf Coatings Gmbh Procede servant a produire un laquage multicouche
CN105848790B (zh) * 2013-12-18 2020-04-28 巴斯夫涂料有限公司 制备多涂层油漆体系的方法
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JP4141498B2 (ja) 2008-08-27
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DE19652841A1 (de) 1997-06-26
AU717221B2 (en) 2000-03-23
WO1997023307A1 (fr) 1997-07-03
EP0871552B1 (fr) 2000-07-12
JP2000501994A (ja) 2000-02-22
ES2150153T3 (es) 2000-11-16
AU1374697A (en) 1997-07-17
BR9612272A (pt) 1999-09-21
AR005262A1 (es) 1999-04-28
KR19990076644A (ko) 1999-10-15
CA2241071A1 (fr) 1997-07-03
TW473528B (en) 2002-01-21
ATE194513T1 (de) 2000-07-15
CN1207693A (zh) 1999-02-10

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